JPH08199376A - Surface-treating agent of copper and copper alloy - Google Patents
Surface-treating agent of copper and copper alloyInfo
- Publication number
- JPH08199376A JPH08199376A JP1312395A JP1312395A JPH08199376A JP H08199376 A JPH08199376 A JP H08199376A JP 1312395 A JP1312395 A JP 1312395A JP 1312395 A JP1312395 A JP 1312395A JP H08199376 A JPH08199376 A JP H08199376A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- hydrogen peroxide
- phosphoric acid
- acid
- treating agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は銅及び銅合金の表面処理
剤に関し、特にプリント配線板の製造工程で用いられる
銅及び銅合金の表面処理剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for copper and copper alloys, and more particularly to a surface treatment agent for copper and copper alloys used in the manufacturing process of printed wiring boards.
【０００２】[0002]
【従来の技術】近年、電子機器の小型化，軽量化，多機
能化によりプリント配線板は技術的な壁を一歩づつ着実
に克服し電子機器の実装部品として益々その重要性を高
めている。電子部品の実装の自動化とともにプリント配
線板のラインのファイン化，穴の小径化，更には多層化
を進め、いわゆる高密度回路形成技術の向上が一層求め
られている。現在、プリント配線板は高密度化に伴い銅
張積層板を種々加工した後、無電解銅めっきなどの各種
めっきを施す工程が増えてきている。この場合、（１）
銅張積層板の銅箔表面に残存している防錆剤や酸化皮膜
の除去、（２）銅表面を活性化させめっきの密着力性を
向上させるための銅表面の粗面化、（３）整面で生じる
きずの除去等、いわゆるソフトエッチング工程が重要な
役割を果たしている。また、プリント配線板の回路パタ
ーンのファイン化に伴い、従来の機械またはパーミス研
磨が技術的に困難になっており、これらの研磨に替わる
化学クリーニングが望まれている。従来から、ソフトエ
ッチング剤としては、過硫酸アンモニュームや過硫酸ナ
トリウムが用いられているが過硫酸アンモニュームでは
廃液中にアンモニュームイオンが共存するため、中和処
理時に銅アンモニューム錯塩が生成し排水中の銅の除去
が困難であるという課題がある。また、過硫酸ナトリウ
ムは、排水の問題はないものの性能面で過硫酸アンモニ
ュームに及ばず、種々工夫をしなければならない事、更
に過硫酸アンモニューム，過硫酸ナトリウムによるソフ
トエッチング液は寿命が短く、建浴回数も多くなり製造
コストが高くなる等の課題がある。2. Description of the Related Art In recent years, printed wiring boards have steadily overcame technological barriers step by step due to miniaturization, weight reduction and multifunctionalization of electronic equipment, and their importance as mounting parts for electronic equipment has been increasing. There is a further demand for improvement of so-called high-density circuit formation technology by automating the mounting of electronic components, finer lines on printed wiring boards, smaller holes, and more layers. At present, as the density of printed wiring boards increases, the number of processes for performing various platings such as electroless copper plating after the copper-clad laminates are variously processed is increasing. In this case, (1)
Removal of the rust preventive agent and oxide film remaining on the copper foil surface of the copper clad laminate, (2) roughening of the copper surface to activate the copper surface and improve the adhesion of the plating, (3 ) A so-called soft etching process plays an important role such as removal of flaws generated on the surface. Further, as the circuit pattern of a printed wiring board becomes finer, conventional mechanical or permis polishing becomes technically difficult, and chemical cleaning in place of these polishings is desired. Conventionally, ammonium persulfate and sodium persulfate have been used as soft etching agents.However, since ammonium persulfate coexists with ammonium ions in the waste liquid, copper ammonium complex salts are generated during the neutralization process. There is a problem that it is difficult to remove copper in wastewater. In addition, sodium persulfate does not have the problem of drainage, but it does not reach the performance of ammonium persulfate in terms of performance, and various measures must be taken. However, there is a problem that the number of baths is increased and the manufacturing cost is increased.
【０００３】このような課題を排除するために、酸性過
酸化水素水溶液によるソフトエッチングが適用されてい
る。しかしながら、従来知られた酸性過酸化水素水溶液
には次の様な課題がある。In order to eliminate such problems, soft etching using an acidic hydrogen peroxide solution is applied. However, the conventionally known aqueous solution of acidic hydrogen peroxide has the following problems.
【０００４】ソフトエッチング後の銅の表面に酸化膜
が生成する為、後処理として希硫酸や希塩酸に浸漬させ
溶解除去する二段処理が必要である。Since an oxide film is formed on the surface of copper after soft etching, a two-step treatment of dipping it in dilute sulfuric acid or dilute hydrochloric acid to dissolve and remove it is necessary as a post-treatment.
【０００５】ソフトエッチングの液の過酸化水素の濃
度変化によって、銅の溶解速度が影響を受けやすく銅表
面仕上がりも不安定になる。A change in the concentration of hydrogen peroxide in the soft-etching solution is likely to affect the dissolution rate of copper, resulting in an unstable copper surface finish.
【０００６】過硫酸アンモニュームによるソフトエッ
チングと比べるとめっき密着性が劣る。Plating adhesion is inferior as compared with soft etching using ammonium persulfate.
【０００７】機械研磨に替わる化学研磨方法としては、
前述の通り酸性過酸化水素系の研磨が提案されている
が、一般に、この方法では、過酸化水素，硫酸で一度酸
化膜を作り、次いで希薄酸水溶液で酸化膜を除去すると
いう二段処理が必要である。これを改良する方法とし
て、上記組成物にリン酸とアミンを添加して一回の処理
で化学研磨する方法が特公昭５３−３２３３９号公報，
特公昭５３−３２３４０号公報で提案されている。しか
し、これらの方法は過酸化水素濃度が５０％から６０％
と高く経済的でない事、更にリン酸やアミンを添加して
も酸化皮膜が完全には除去出来ない等、高密度のプリン
ト配線板用には適用出来ないという課題があった。As a chemical polishing method replacing mechanical polishing,
As mentioned above, polishing with an acidic hydrogen peroxide system has been proposed. Generally, however, in this method, a two-step treatment of once forming an oxide film with hydrogen peroxide and sulfuric acid and then removing the oxide film with a dilute aqueous acid solution is performed. is necessary. As a method for improving this, a method of adding phosphoric acid and amine to the above composition and chemically polishing the composition in a single treatment is disclosed in JP-B-53-32339.
It is proposed in JP-B-53-32340. However, these methods have a hydrogen peroxide concentration of 50% to 60%.
There is a problem that it cannot be applied to high-density printed wiring boards, such as that it is not very economical and that even if phosphoric acid or amine is added, the oxide film cannot be completely removed.
【０００８】一方、特公平２−１２５８８６号公報で
は、プリント基板のエッチングで用いる過酸化水素用安
定剤としてペンゾチアゾイルチオプロピレンスルホン酸
ナトリウム系の過酸化水素安定剤が提案されているが、
銅表面のエッチング後の仕上り状況は良好ではないとい
う課題がある。On the other hand, Japanese Patent Publication No. 2-125886 proposes a sodium penzothiazoyl thiopropylene sulfonate type hydrogen peroxide stabilizer as a hydrogen peroxide stabilizer used for etching a printed circuit board.
There is a problem that the finished condition of the copper surface after etching is not good.
【０００９】また、特公平２−２３６２８９号公報で
は、硫酸１００〜１５０ｇ／Ｌ，過酸化水素１０〜５０
ｇ／Ｌ，及びりん酸０．５ｇ／Ｌ以上からなる酸性過酸
化水素水溶液にピペリジンまたはその誘導体を０．１ｇ
／Ｌ以上含有せしめる銅および銅合金の表面処理剤が提
案されており、良好な銅−銅の密着性，エッチング後に
平滑された光沢性のあることが報告されているが、銅濃
度が４０ｇ／Ｌを超える領域で過酸化水素の無効分解が
多くなり製造コストが高くなるという課題がある。Further, in Japanese Patent Publication No. 2-236289, 100-150 g / L of sulfuric acid and 10-50 of hydrogen peroxide are used.
0.1 g of piperidine or its derivative in an acidic aqueous hydrogen peroxide solution containing g / L and phosphoric acid of 0.5 g / L or more
/ L or more surface treatment agents for copper and copper alloys have been proposed, and good copper-copper adhesion and smoothness after etching have been reported, but the copper concentration was 40 g / In a region exceeding L, there is a problem that hydrogen peroxide is ineffectively decomposed to increase the manufacturing cost.
【００１０】更に、特公平３−１４０４８１号公報，特
公平３−１４０４８２号公報では、銅張り板の表面を硫
酸１２０〜１７０ｇ／Ｌ，過酸化水素３０〜８０ｇ／
Ｌ，添加剤２０〜５０ｇ／Ｌからなる処理液で処理する
ことにより整面処理を安定化し、更に過酸化水素の分解
を抑制するという方法が提案されており、また、特公平
３−１４０４８３号公報では、上記組成の処理組成の処
理液に更に銅イオンを１ｇ／Ｌ以上添加することにより
均一な凹凸粗化面が得られるという報告が、また、特公
平３−１４０４８４号公報では、建浴後３０〜５０℃で
１０分間以上熟成することにより、均一な凹凸粗化面が
得られるという報告がある。これらに関しては、やはり
銅濃度が４０ｇ／Ｌを超える領域で過酸化水素の無効分
解が多くなり製造コストが高くなるという課題がある。Further, in Japanese Patent Publication No. 3-140481 and Japanese Patent Publication No. 3-140482, 120 to 170 g / L of sulfuric acid and 30 to 80 g / L of hydrogen peroxide are used on the surface of the copper-clad plate.
A method has been proposed in which the surface treatment is stabilized by treating with a treatment liquid containing L and 20 to 50 g / L of additive, and the decomposition of hydrogen peroxide is further suppressed, and JP-B-3-140483. In the publication, it is reported that a uniform roughened surface can be obtained by further adding 1 g / L or more of copper ion to the treatment solution having the above-mentioned composition, and in Japanese Patent Publication No. 3-140484, after the bath is built. There is a report that a uniform roughened and roughened surface can be obtained by aging at 30 to 50 ° C. for 10 minutes or more. With respect to these, there is still a problem that hydrogen peroxide is ineffectively decomposed in a region where the copper concentration exceeds 40 g / L and the manufacturing cost becomes high.
【００１１】[0011]
【発明が解決しようとする課題】以上説明したように従
来の銅及び銅合金の表面処理剤では下記に列挙する課題
がある。As described above, the conventional surface treating agents for copper and copper alloys have the following problems.
【００１２】（１）中和処理時に銅アンモニウム錯塩が
生成し排水中の銅の除去が困難である。(1) Copper ammonium complex salt is generated during the neutralization process, and it is difficult to remove copper in the waste water.
【００１３】（２）寿命が短く、建浴回数も多くなり製
造コストが高くなる。(2) The life is short, the number of baths is increased, and the manufacturing cost is increased.
【００１４】（３）二段処理が必要で銅表面仕上りが不
安定でめっき密着性が劣る。(3) The two-step treatment is required, the copper surface finish is unstable, and the plating adhesion is poor.
【００１５】（４）経済的でなく、酸化皮膜が完全に除
去できず高密度のプリント配線板には適用できない。(4) It is not economical and cannot be applied to a high-density printed wiring board because the oxide film cannot be completely removed.
【００１６】（５）過酸化水素の無効分解が多く、製造
コストが高くなる。(5) Since hydrogen peroxide is often ineffectively decomposed, the manufacturing cost becomes high.
【００１７】本発明の目的は、排水中の銅の除去が容易
で、過酸化水素の無効分解が低く優れた安定性を示し製
造コストが安価でしかも銅表面仕上りが良好で酸化皮膜
の生成が抑制でき、高密度のプリント配線板に適用でき
る銅及び銅合金の表面処理剤を提供することにある。The object of the present invention is to easily remove copper in waste water, to reduce the ineffective decomposition of hydrogen peroxide, to exhibit excellent stability, to reduce the manufacturing cost, to obtain a good copper surface finish, and to form an oxide film. It is an object of the present invention to provide a copper and copper alloy surface treatment agent which can be suppressed and can be applied to a high-density printed wiring board.
【００１８】[0018]
【課題を解決するための手段】前記の様な課題を解決す
る手段として、本発明は、過酸化水素，硫酸及びリン酸
からなる過酸化水素水溶液にブチルジグリコール或るい
はブチルセロソルブのいずれかを０．１／ｇＬ以上アセ
トアニリド，アジピン酸，ゼラチンの内少なくとも２種
類以上を０．０１〜０．５ｇ／Ｌの範囲で含有せしめて
なる銅および銅合金の表面処理剤である。この表面処理
剤により処置して水洗した後の銅および銅合金は酸化皮
膜の生成がなく、その結果従来必要とされていた酸化皮
膜除去の後処理工程が省けると共にめっきの密着性，は
んだ濡れ性，光沢性に優れる等性能面でも顕著な効果を
示す。本発明で使用されるリン酸は０．５ｇ／Ｌ以上の
添加量で酸化皮膜の生成を抑制する効果を発揮するが特
に２〜５ｇ／Ｌの範囲の添加が望ましい。５ｇ／Ｌでも
効果はあり上限は特に限定されないが多すぎると経済性
に劣ることになり好ましくない。０．５ｇ／Ｌ以上のリ
ン酸の添加により酸化皮膜生成の抑制効果は示すが、硫
酸，過酸化水素，リン酸だけの組成からなる過酸化水素
溶液を用いた場合には、その後の酸化皮膜除去工程を省
く迄には至らない。また、過酸化水素の安定性は、銅濃
度が増加するに従い顕著に悪化し、過酸化水素の無効分
解率が増加するが、本発明は、酸性過酸化水素溶液にリ
ン酸を加え、更にブチルジグリコール或いはブチルセロ
ソルブと、アセトアニリド，アジピン酸，ゼラチンの内
の２種類の添加剤からなる混合液を加えることにより、
銅濃度が増加した場合でも、顕著な過酸化水素の安定性
を保つと同時に、酸化皮膜を完全に抑制する特異的効果
のあることを見いだした点に特徴がある。As a means for solving the above-mentioned problems, the present invention provides a hydrogen peroxide aqueous solution containing hydrogen peroxide, sulfuric acid and phosphoric acid containing either butyl diglycol or butyl cellosolve. A surface treating agent for copper and copper alloys containing at least two kinds of acetanilide, adipic acid, and gelatin in an amount of 0.01 to 0.5 g / L in a range of 0.01 to 0.5 g / L. After treatment with this surface treatment agent and washing with water, copper and copper alloys do not form an oxide film. As a result, the post-treatment process required to remove an oxide film, which was conventionally required, can be omitted, and the adhesion and solder wettability of plating can be eliminated. , It also has remarkable effects in terms of performance such as excellent gloss. The phosphoric acid used in the present invention exerts an effect of suppressing the formation of an oxide film at an addition amount of 0.5 g / L or more, but it is particularly preferable to add it in the range of 2 to 5 g / L. Even if the amount is 5 g / L, the effect is obtained and the upper limit is not particularly limited, but if it is too large, the economy is deteriorated, which is not preferable. The addition of 0.5 g / L or more of phosphoric acid shows an effect of suppressing the formation of an oxide film, but when a hydrogen peroxide solution consisting of only sulfuric acid, hydrogen peroxide and phosphoric acid is used, the subsequent oxide film is formed. It is not possible to omit the removal process. Further, the stability of hydrogen peroxide is markedly deteriorated as the copper concentration is increased, and the ineffective decomposition rate of hydrogen peroxide is increased. By adding a mixed solution of diglycol or butyl cellosolve and two kinds of additives of acetanilide, adipic acid and gelatin,
It is characterized by the fact that even when the copper concentration is increased, the remarkable stability of hydrogen peroxide is maintained and, at the same time, the specific effect of completely suppressing the oxide film is found.
【００１９】本発明の表面処理剤は必要に応じ他の適宜
の添加剤を含有しうる。その具体例としては、過酸化水
素の安定剤として知られるアルコール類，フェノール
類，グリコールエーテル類等である。本発明の表面処理
剤はこれらの安定剤等の添加剤によって悪影響を受ける
ことはない。The surface treating agent of the present invention may contain other appropriate additives as required. Specific examples thereof include alcohols, phenols, glycol ethers and the like which are known as stabilizers for hydrogen peroxide. The surface treatment agent of the present invention is not adversely affected by additives such as these stabilizers.
【００２０】本発明の表面処理剤は、プリント配線板製
造工程の内、次のような広範囲の工程に適応出来るとい
う特徴も有する。The surface treatment agent of the present invention is also characterized in that it can be applied to the following wide range of processes in the manufacturing process of printed wiring boards.
【００２１】（１）一時銅めっき前処理（２）二次銅め
っき前処理（３）フォト印刷前処理（４）ソルダレジス
ト印刷の前処理（５）ハンダコートの前処理（６）仕上
げ処理（７）内層フォト前処理（８）機械研磨に替わる
化学クリーニング（９）ソフトエッチングによる銅厚制
御（１０）治工具のエッチング処理本発明の表面処理剤
を使用する際の液温は一般的には５０℃以下であり、好
ましくは３０〜４０℃の範囲である。５０℃以上になる
と、過酸化水素の分解量が多くなり液管理が難しくなる
ので好ましくない。また、表面処理剤の付与手段として
は、浸漬法，スプレィ法，浸漬揺動法，反転スプレィ法
等の公知の手段を用いることができる。(1) Pretreatment for temporary copper plating (2) Pretreatment for secondary copper plating (3) Pretreatment for photo printing (4) Pretreatment for solder resist printing (5) Pretreatment for solder coat (6) Finishing treatment ( 7) Inner layer photo pretreatment (8) Chemical cleaning instead of mechanical polishing (9) Copper thickness control by soft etching (10) Etching treatment of jigs and liquids The liquid temperature when using the surface treatment agent of the present invention is generally The temperature is 50 ° C or lower, preferably 30 to 40 ° C. When the temperature is 50 ° C. or higher, the amount of hydrogen peroxide decomposed increases, and it becomes difficult to manage the liquid. As the means for applying the surface treatment agent, known means such as a dipping method, a spraying method, a dipping rocking method, and an inversion spraying method can be used.
【００２２】[0022]
【実施例】次に、本発明の実施例について説明する。EXAMPLES Next, examples of the present invention will be described.
【００２３】表１に本発明の第１の実施例の組成と銅濃
度６０ｇ／Ｌ，４０℃での放置時間と過酸化水素と無効
分解率及び表面仕上り状態を示す。第１の実施例は、表
１に示すように、硫酸１２０ｇ／Ｌ，過酸化水素３５ｇ
／Ｌ，リン酸０．５ｇ／Ｌからなる組成の水溶液に、ま
ず、水１容に対してブチルジグリコール１容の割合で混
合し、その混合液を４０〜８０℃迄昇温し、撹伴しなが
らアセトアニリドを２００ｇ／Ｌ，アジピン酸を２００
ｇ／Ｌとなるように調合する。その後、硫酸−過酸化水
素エッチング液に上記の調合液を０．１％添加し第１の
実施例とし、表１に示すように、銅濃度６０ｇ／Ｌ，４
０℃での放置時間２４Ｈ，４８Ｈ，７２Ｈにおける過酸
化水素の無効分解率と表面仕上り状態を調査した。その
結果を表１に示す。なお、比較用として、リン酸０．５
ｇ／Ｌ，ピペリジン０．５ｇ／Ｌ添加した従来の比較用
１，リン酸０．５ｇ／Ｌ，ブチルジグリコール０．５ｇ
／Ｌ，アジピン酸０．２ｇ／Ｌ添加した従来の比較用２
の調査結果についても併記した。Table 1 shows the composition of the first embodiment of the present invention, the standing time at a copper concentration of 60 g / L and 40 ° C., hydrogen peroxide, ineffective decomposition rate and surface finish state. In the first embodiment, as shown in Table 1, sulfuric acid 120 g / L, hydrogen peroxide 35 g
/ L, phosphoric acid 0.5 g / L, and an aqueous solution having a composition of 1 volume of butyldiglycol to 1 volume of water, and the mixture is heated to 40 to 80 ° C and stirred. Acetanilide 200 g / L and adipic acid 200
Formulate to be g / L. After that, 0.1% of the above-mentioned prepared solution was added to a sulfuric acid-hydrogen peroxide etching solution to make a first example, and as shown in Table 1, copper concentration was 60 g / L, 4
The ineffective decomposition rate of hydrogen peroxide and the surface finish state at standing times of 24 hours, 48 hours and 72 hours at 0 ° C. were investigated. Table 1 shows the results. For comparison, phosphoric acid 0.5
g / L, Piperidine 0.5 g / L added for conventional comparison 1, Phosphoric acid 0.5 g / L, Butyldiglycol 0.5 g
/ L, adipic acid 0.2g / L conventional comparison 2
The results of the survey are also shown.
【００２４】[0024]
【表１】 [Table 1]
【００２５】この結果、第１の実施例は、放置時間２４
Ｈ，４８Ｈ，７２Ｈともに従来の比較用１，比較用２と
比較し過酸化水素の無効分解率が改善され安定性を示
し、表面仕上り状態も平滑された光沢性のあることが確
認できた。As a result, in the first embodiment, the leaving time is 24 hours.
It was confirmed that H, 48H, and 72H had improved ineffective decomposition rate of hydrogen peroxide and showed stability as compared with the conventional Comparative 1 and Comparative 2 and that the surface finish was smooth and glossy.
【００２６】表２に本発明の第２の実施例の組成と銅濃
度６０ｇ／Ｌ，４０℃での放置時間と過酸化水素の無効
分解率及び表面仕上り状態を示す。第２の実施例は表２
に示すように、硫酸１２０ｇ／Ｌ，過酸化水素３５ｇ／
Ｌ，リン酸０．５ｇ／Ｌからなる組成の水溶液に、ま
ず、水１容に対してブチルセロソルブ１容の割合で混合
し、その混合液を４０〜８０℃迄昇温し、撹伴しながら
アセドアニリドを１００ｇ／Ｌ，ゼラチンを１００ｇ／
Ｌとなるように調合する。その後、硫酸−過酸化水素エ
ッチング液に上記の調合液を０．２％添加し第２の実施
とし、表２に示すように、銅濃度６０ｇ／Ｌ，４０℃で
の放置時間２４Ｈ，４８Ｈ，７２Ｈにおける過酸化水素
の無効分解率と表面仕上り状態を調査した。その結果を
表２に示す。なお、比較用として、リン酸０．５ｇ／
Ｌ，ピペリジン０．５ｇ／Ｌ添加した従来の比較用１，
リン酸０．５ｇ／Ｌ，ブチルセロソルブ０．５ｇ／Ｌ，
アセトアニリド０．２ｇ／Ｌ添加した従来の比較用３の
調査結果についても併記した。Table 2 shows the composition of the second embodiment of the present invention, the standing time at a copper concentration of 60 g / L and 40 ° C., the ineffective decomposition rate of hydrogen peroxide, and the surface finish state. The second embodiment is Table 2
As shown in, sulfuric acid 120 g / L, hydrogen peroxide 35 g /
First, an aqueous solution having a composition of L and phosphoric acid 0.5 g / L was mixed at a ratio of 1 volume of butyl cellosolve to 1 volume of water, and the mixed solution was heated to 40 to 80 ° C. with stirring. Acetanilide 100 g / L, gelatin 100 g / L
Formulate to L. After that, 0.2% of the above-mentioned prepared solution was added to the sulfuric acid-hydrogen peroxide etching solution to make the second implementation. As shown in Table 2, the copper concentration was 60 g / L, the standing time at 40 ° C. was 24 H, 48 H, The ineffective decomposition rate of hydrogen peroxide at 72H and the surface finish state were investigated. The results are shown in Table 2. For comparison, phosphoric acid 0.5 g /
L, Piperidine 0.5 g / L added for conventional comparison 1,
Phosphoric acid 0.5 g / L, butyl cellosolve 0.5 g / L,
The results of the investigation of the conventional comparative 3 containing 0.2 g / L of acetanilide are also shown.
【００２７】[0027]
【００２８】[0028]
【表２】 [Table 2]
【００２９】この結果、第２の実施例は、放置時間２４
Ｈ，４８Ｈ，７２Ｈともに従来の比較例１，比較例３と
比較し過酸化水素分解率が改善され、さらに第１の実施
例よりも優れていることが確認され、表面仕上り状態も
平滑された光沢性のあることも確認できた。As a result, in the second embodiment, the standing time is 24 hours.
It was confirmed that H, 48H, and 72H had a higher hydrogen peroxide decomposition rate than those of Comparative Examples 1 and 3 of the related art, and were superior to those of the first example, and the surface finish was smoothed. It was also confirmed that it was glossy.
【００３０】表３に本発明の第３の実施例の組成と銅濃
度６０ｇ／Ｌ，４０℃での放置時間と過酸化水素の無効
分解率及び表面仕上り状態を示す。第３の実施例は表３
に示すように、硫酸１２０ｇ／Ｌ，過酸化水素３５ｇ／
Ｌ，リン酸０．５ｇ／Ｌからなる組成の水溶液に、ま
ず、水１容に対してブチルジグリコール１容の割合で混
合し、その混合液を４０〜８０℃迄昇温し、撹伴しなが
らアジピン酸を５００ｇ／Ｌ，ゼラチンを３０ｇ／Ｌと
なるように調合する。その後、硫酸−過酸化水素エッチ
ング液に上記の調合液を０．１％添加し第３の実施例と
し、表３に示すように、銅濃度６０ｇ／Ｌ，４０℃での
放置時間２４Ｈ，４８Ｈ，７２Ｈにおける過酸化水素の
無効分解率と表面仕上り状態を調査した。その結果を表
３に示す。なお、比較用としてリン酸０．５ｇ／Ｌ，ピ
ペリジン０．５ｇ／Ｌ添加した従来の比較用１の調査結
果にていても併記した。Table 3 shows the composition of the third embodiment of the present invention, the standing time at a copper concentration of 60 g / L and 40 ° C., the ineffective decomposition rate of hydrogen peroxide, and the surface finish state. Table 3 shows the third embodiment.
As shown in, sulfuric acid 120 g / L, hydrogen peroxide 35 g /
First, an aqueous solution of L and 0.5 g / L of phosphoric acid was mixed at a ratio of 1 volume of butyldiglycol to 1 volume of water, and the mixture was heated to 40 to 80 ° C. and stirred. Meanwhile, adipic acid is mixed at 500 g / L and gelatin is mixed at 30 g / L. Then, 0.1% of the above-mentioned prepared solution was added to the sulfuric acid-hydrogen peroxide etching solution to make a third example, and as shown in Table 3, the copper concentration was 60 g / L, the standing time at 40 ° C. was 24H, 48H. , 72H, the ineffective decomposition rate of hydrogen peroxide and the surface finish state were investigated. Table 3 shows the results. For comparison, the results of the investigation of the conventional Comparative 1 in which phosphoric acid 0.5 g / L and piperidine 0.5 g / L were added were also described.
【００３１】[0031]
【表３】 [Table 3]
【００３２】この結果第３の実施例は、放置時間２４
Ｈ，４８Ｈ，７２Ｈともに従来の比較用１と比較して過
酸化水素の無効分解率が改善され、さらに、第１の実施
例，第２の実施例よりも優れていることが確認され、表
面仕上り状態も平滑化された光沢性のあることも確認で
きた。As a result, the third embodiment shows that the standing time is 24 hours.
It was confirmed that H, 48H, and 72H each had an improved ineffective decomposition rate of hydrogen peroxide as compared with the conventional Comparative Example 1, and were superior to the first and second examples. It was also confirmed that the finished state was smooth and glossy.
【００３３】[0033]
【発明の効果】以上説明したように本発明は、過酸化水
素，硫酸及びリン酸からなる過酸化水素水溶液にブチル
ジグリコール或はブチルセロソルブのいずれかを０．１
ｇ／Ｌ以上、アセトアニリド，アジピン酸，ゼラチンの
内の少くとも２種類以上を０．０１〜０．０５ｇ／Ｌの
範囲で含有させることにより、銅濃度が増加した場合で
も優れた過酸化水素の安定性を示し、従来の銅及び銅合
金の表面処理剤と比較して無効分解率を半減し過酸化水
素の安定性を保つとともに、経済的効果を高めることが
できる。また、ソフトエッチング後の銅の表面は平滑さ
れた光沢を持ち、酸化皮膜を抑制する効果がある。As described above, according to the present invention, butyldiglycol or butylcellosolve is added to an aqueous solution of hydrogen peroxide consisting of hydrogen peroxide, sulfuric acid and phosphoric acid in an amount of 0.1%.
g / L or more, and at least two or more of acetanilide, adipic acid, and gelatin in the range of 0.01 to 0.05 g / L provide excellent hydrogen peroxide even when the copper concentration is increased. It exhibits stability and can reduce the ineffective decomposition rate by half as compared with conventional surface treatment agents for copper and copper alloys, maintain the stability of hydrogen peroxide, and enhance the economic effect. Further, the copper surface after soft etching has a smooth gloss, and has an effect of suppressing an oxide film.
Claims (3)
６０〜５００ｇ／Ｌ，過酸化水素１０〜５０ｇ／Ｌから
なる酸性過酸化水素水溶液に添加剤としてリン酸を０．
５ｇ／Ｌ以上，ブチルジグリコール，アセトアニリド及
びアジピン酸を０．０１ｇ／Ｌ以上含有せしめてなる事
を特徴とする銅及び銅合金の表面処理剤。1. An acidic hydrogen peroxide aqueous solution containing sulfuric acid and hydrogen peroxide as main components and comprising 60 to 500 g / L of sulfuric acid and 10 to 50 g / L of hydrogen peroxide, and phosphoric acid as an additive in an amount of 0.
A surface-treating agent for copper and copper alloys, containing 5 g / L or more, butyldiglycol, acetanilide, and adipic acid in an amount of 0.01 g / L or more.
６０〜５００ｇ／Ｌ，過酸化水素１０〜５０ｇ／Ｌから
なる酸性過酸化水素水溶液に添加剤としてリン酸を０．
５ｇ／Ｌ以上，ブチルセロソルブ，アセトアニリド及び
ゼラチンを０．０１ｇ／Ｌ以上含有せしめてなる事を特
徴とする銅及び銅合金の表面処理剤。2. Phosphoric acid as an additive is added to an acidic hydrogen peroxide aqueous solution containing sulfuric acid and hydrogen peroxide as main components and comprising 60 to 500 g / L of sulfuric acid and 10 to 50 g / L of hydrogen peroxide.
A surface treatment agent for copper and copper alloys, characterized by containing 5 g / L or more, butyl cellosolve, acetanilide and gelatin in an amount of 0.01 g / L or more.
６０〜５００ｇ／Ｌ，酸性過酸化水素水溶液に添加剤と
してリン酸を０．５ｇ／Ｌ以上，ブチルジグリコール，
アジピン酸及びゼラチンを０．０１ｇ／Ｌ以上含有せし
めてなる事を特徴とする銅及び銅合金の表面処理剤。3. Sulfuric acid and hydrogen peroxide as main components, 60-500 g / L of sulfuric acid, 0.5 g / L or more of phosphoric acid as an additive to an acidic aqueous hydrogen peroxide solution, butyldiglycol,
A surface-treating agent for copper and copper alloys, which comprises 0.01 g / L or more of adipic acid and gelatin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1312395A JP2793515B2 (en) | 1995-01-30 | 1995-01-30 | Copper and copper alloy surface treatment agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1312395A JP2793515B2 (en) | 1995-01-30 | 1995-01-30 | Copper and copper alloy surface treatment agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08199376A true JPH08199376A (en) | 1996-08-06 |
| JP2793515B2 JP2793515B2 (en) | 1998-09-03 |
Family
ID=11824392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1312395A Expired - Fee Related JP2793515B2 (en) | 1995-01-30 | 1995-01-30 | Copper and copper alloy surface treatment agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2793515B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2370251A (en) * | 2000-12-20 | 2002-06-26 | Lg Philips Lcd Co Ltd | Etchant and array substrate having copper lines etched by the etchant |
| JP2003519286A (en) * | 2000-01-07 | 2003-06-17 | エレクトロケミカルズ インコーポレイティド | Method for roughening copper surface for bonding to substrate |
| GB2386865A (en) * | 2000-12-20 | 2003-10-01 | Lg Philips Lcd Co Ltd | Etchant for array substrate having copper lines |
-
1995
- 1995-01-30 JP JP1312395A patent/JP2793515B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003519286A (en) * | 2000-01-07 | 2003-06-17 | エレクトロケミカルズ インコーポレイティド | Method for roughening copper surface for bonding to substrate |
| JP4754752B2 (en) * | 2000-01-07 | 2011-08-24 | オーエムジー エレクトロニック ケミカルズ，リミティド ライアビリティ カンパニー | Method of roughening a copper surface for bonding to a substrate |
| GB2370251A (en) * | 2000-12-20 | 2002-06-26 | Lg Philips Lcd Co Ltd | Etchant and array substrate having copper lines etched by the etchant |
| GB2386865A (en) * | 2000-12-20 | 2003-10-01 | Lg Philips Lcd Co Ltd | Etchant for array substrate having copper lines |
| GB2370251B (en) * | 2000-12-20 | 2003-12-03 | Lg Philips Lcd Co Ltd | Etchant and array substrate having copper lines etched by the etchant |
| US6780784B2 (en) | 2000-12-20 | 2004-08-24 | Lg. Philips Lcd Co., Ltd. | Etchant and array substrate having copper lines etched by the etchant |
| GB2386865B (en) * | 2000-12-20 | 2004-09-15 | Lg Philips Lcd Co Ltd | Etchant and array substrate having copper lines etched by the etchant |
| US7850866B2 (en) | 2000-12-20 | 2010-12-14 | Lg Display Co., Ltd. | Etchant and array substrate having copper lines etched by the etchant |
| US8236704B2 (en) | 2000-12-20 | 2012-08-07 | Lg Display Co., Ltd. | Etchant and array substrate having copper lines etched by the etchant |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2793515B2 (en) | 1998-09-03 |
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